CN102066471B - Hardcoat film for molding - Google Patents

Hardcoat film for molding Download PDF

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Publication number
CN102066471B
CN102066471B CN200980123310.XA CN200980123310A CN102066471B CN 102066471 B CN102066471 B CN 102066471B CN 200980123310 A CN200980123310 A CN 200980123310A CN 102066471 B CN102066471 B CN 102066471B
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China
Prior art keywords
film
molding
quality
hard coat
ionizing radiation
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CN200980123310.XA
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CN102066471A (en
Inventor
泽田薰
森宪一
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Toyobo Co Ltd
Toyo Textile Co Ltd
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Toyo Textile Co Ltd
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter

Abstract

Disclosed is a hardcoat film for molding, which has both high surface hardness and moldability. Specifically disclosed is a hardcoat film for molding, which has a hardcoat layer on at least one side of a base film. The hardcoat layer is obtained by coating and curing a coating liquid. The coating liquid contains at least an ionizing radiation curable compound having three or more functional groups and a monofunctional and/or bifunctional ionizing radiation curable compound. The content of the monofunctional and/or bifunctional ionizing radiation curable compound in the ionizing radiation curable compounds contained in the coating liquid is not less than 5% by mass but not more than 95% by mass.

Description

Hardcoat film for molding
Technical field
The present invention relates to also good hardcoat film for molding of the good and formability of surface hardness, scuff resistance.
Background technology
In the past, as molding film, polychloroethylene film is representative, in recent years due to environment resistant needs, using (for example, referring to Patent Document 1～10) such as unstretching film that the polyester little by carrying capacity of environment, polycarbonate and acrylic resin form and thermotolerance, biaxially oriented polyester films that solvent resistance is good.
For example, the label of household electrical appliances, automobile with or building materials member etc., in the time that the position installation forming of itself and external contact is used film, in order to prevent from making scar, improve scuff resistance as object to strengthen the surface hardness of molding film, on surface, hard coat is set.
As the method that hard coat is set on molding film, by pressing after the moulding such as the empty method of forming, vacuum forming, utilize impregnation method, spray pattern etc. to carry out post-treatment and the method for lamination hard coat is conventional method.But in aforesaid method, due to lamination hard coat in wafer processes, therefore the raising of production rate exists the limit, and have problems aspect the stability of quality.Therefore, need to be by arranging and carry out the formed body that the method for moulding obtains after hard coat in volume to volume mode on the film before moulding.
Before moulding the mode of lamination hard coat, as the desired characteristic of hard coat, the mode of hard coat is set in the post-treatment after shaping and the surface hardness of equal extent, scuff resistance are necessary, needs to follow in addition the formability of the distortion while following moulding.But firmly resinize in the situation that, in order to meet surface hardness, hard coat is really up to the mark, therefore there is no formability common, the distortion hard coat while producing along with forming process cracks the problem of (fracture of hard coat).
At this, the resin that has proposed also have surface hardness to a certain degree after solidifying by lamination and had a flexibility improves the hard coat film of formability and has strong surface hardness and bendability hard coat film (patent documentation 11～14) by the layer of pressing multilayer to have the layer of flexibility at layers on substrates and have a strong surface hardness.
Patent documentation 1: Japanese kokai publication hei 9-156267 communique
Patent documentation 2: Japanese kokai publication hei 9-187903 communique
Patent documentation 3: Japanese kokai publication hei 10-296937 communique
Patent documentation 4: Japanese kokai publication hei 11-268215 communique
Patent documentation 5: TOHKEMY 2001-129951 communique
Patent documentation 6: TOHKEMY 2001-212868 communique
Patent documentation 7: TOHKEMY 2002-249652 communique
Patent documentation 8: TOHKEMY 2003-211606 communique
Patent documentation 9: TOHKEMY 2004-075713 communique
Patent documentation 10: TOHKEMY 2005-290354 communique
Patent documentation 11: TOHKEMY 2005-305383 communique
Patent documentation 12: TOHKEMY 2007-284626 communique
Patent documentation 13: TOHKEMY 2007-313728 communique
Patent documentation 14: No. 2008/029666 brochure of International Publication
Summary of the invention
But, the hard coat film proposing in patent documentation 11,13, although there is suitable surface hardness, but for formability, only there is bendability, stamping-out is processed the processing characteristics of this restriction, the hard coat film proposing in patent documentation 12, although have extensibility, can not meet surface hardness.In addition, the hard coat film proposing in patent documentation 14, although attempt taking into account surface hardness and plasticity, in the field that requires higher plasticity, higher surface hardness, also existence can not be brought into play the situation of sufficient performance., above-mentioned patent documentation does not provide the hardcoat film for molding that simultaneously meets high surface hardness and high-mouldability two specific characters.
The object of the invention is in order to address the above problem,, provide by processing hard coat and be laminated on molding film before moulding, can contribute to boost productivity, the stability of quality, and both hardcoat film for moldings of formability of distortion when having surface hardness, scuff resistance concurrently and can following moulding.
The inventor conducts in-depth research in order to address the above problem, and result has finally completed the present invention., the present invention is as described below.
The 1st invention is a kind of hardcoat film for molding, it has and at least one surface of base material film, is coated with coating fluid and makes it solidify the hard coat that forms, above-mentioned coating fluid at least contains and has 3 the above ionizing radiation curable compounds of functional group and ionizing radiation curable compounds of 1 and/or 2 functional group, and the content of the ionizing radiation curable compounds of 1 and/or 2 functional group in the contained ionizing radiation curable compounds of above-mentioned coating fluid is that 5 quality % are above and below 95 quality %.
The 2nd invention is above-mentioned hardcoat film for molding, and wherein, above-mentioned base material film is the double axial orientated polyester film that contains copolyester.
The 3rd invention is above-mentioned hardcoat film for molding, and wherein, at least a kind of contained ionizing radiation cured resin of above-mentioned coating fluid is to have amino ionizing radiation cured resin.
The 4th invention is above-mentioned hardcoat film for molding, and wherein, in above-mentioned hard coat, containing median size is the particle more than 10nm and below 300nm, and the content of above-mentioned particle in hard coat is more than 5 quality % and below 70 quality %.
The 5th invention is above-mentioned hardcoat film for molding, wherein, in above-mentioned hard coat, contain ionizing radiation curing type silicone resin, the content of above-mentioned ionizing radiation curing type silicone resin in hard coat is more than 0.15 mass parts and below 15 mass parts with respect to above-mentioned ionizing radiation curable compounds 100 mass parts.
The 6th invention is a kind of formed body, and above-mentioned hardcoat film for molding moulding is formed.
The 7th invention is above-mentioned formed body, and wherein, the thickness of hard coat is more than 0.5 μ m and below 50 μ m.
The 8th invention is a kind of manufacture method of hardcoat film for molding volume, is to have the manufacture method that is coated with coating fluid and makes its hardcoat film for molding volume that solidifies the hard coat forming at least one surface of base material film, it is characterized in that,
Above-mentioned coating fluid at least contains organic solvent, has 3 the above ionizing radiation curable compounds of functional group and ionizing radiation curable compounds of 1 and/or 2 functional group,
The content of the ionizing radiation curable compounds of 1 and/or 2 functional group in the contained ionizing radiation curable compounds of above-mentioned coating fluid is that 5 quality % are above and below 95 quality %,
Being coated with after above-mentioned coating fluid, is more than 50N/m and below 300N/m and temperature is to be dried under the condition more than 40 ℃ and below 120 ℃ at film tension force, then makes it solidify, and hard coat is set thus.
Invention effect
Hardcoat film for molding of the present invention, formability two specific characters of the distortion when thering is surface hardness, scuff resistance and can following moulding.The present invention is in order to have high surface hardness and good extensibility, as preferred embodiment, applicable to such as label use or building materials member etc.In addition, as preferred embodiment of the present invention, in the time that use has amino ionizing radiation cured resin and/or particle, can have better surface hardness and formability two specific characters concurrently, the members such as such as housing of applicable work.And, the present invention does not need the hard painting processing after moulding, can contribute to boost productivity, the stability of quality, as preferred embodiment of the present invention at the manufacture view of forming process, in the situation that using molding film volume, the excellent in stability of the quality of formed body.
Embodiment
1) formation of the coating that contains tin
Below, the present invention is at length described.
(base material film)
In the present invention, base material film does not have special restriction, but is characterised in that to have formability.At this, formability refers to by mould molding, presses the forming process such as empty moulding, vacuum forming can form formed body.Particularly, in the part of extending partly by moulding, even while partly producing high stress, base material film does not also rupture, and there is the membrane stress characteristic that can form formed body.
As this base material film, the material that can enumerate the plastic film of polyester such as, acrylic acid or the like, cellulose family, polyethylene kind, polypropylene-base, polyolefins, polyvinyl chloride, polycarbonate-based, phenols, amino formate etc. or sheet and any two or more laminating in these is obtained.The preferably good polyester film of the balance of thermotolerance, flexibility.
As base material film, the preferably good polyester film that contains copolyester of formability when hot briquetting under low temperature, low pressure.As copolyester, the copolyester that preferably (a) is made up of aromatic dicarboxylic acid composition and the diol component that contains ethylene glycol, a chain aliphatic diol or alicyclic diol or (b) copolyester that formed by the aromatic dicarboxylic acid composition that contains terephthalic acid and m-phthalic acid and the diol component that contains ethylene glycol.
As above-mentioned copolyester, in the time using the copolyester being formed by aromatic dicarboxylic acid composition and the diol component that contains ethylene glycol, chain aliphatic diol or alicyclic diol, as aromatic dicarboxylic acid composition, preferably terephthalic acid, m-phthalic acid, naphthalic acid or their ester formative derivative, with respect to dicarboxylic acid composition total amount, the amount of terephthalic acid and/or naphthalic acid composition is more than 70mol%, preferably more than 85mol%, particularly preferably more than 95mol%, most preferably 100mol%.
In the present invention, the polyester film that contains copolyester, contains the constituent of copolyester composition as film, as concrete mode, can illustrate following polyester film.(1) base material film is all formed by copolyester; (2) for example contain copolyester, as the part of the constituent of base material film (, being formed by the resin combination that other (all) polyester such as copolyester and polyethylene terephthalate or PEN are obtained by mixing); (3) base material film is by the polyester layer that contains copolyester with do not form containing the polyester layer multilayer of copolyester.
From the viewpoint of thermotolerance and solvent resistance etc., particularly preferably biaxially-stretched film of above-mentioned base material film.As drawing process, can enumerate pipe stretching method, simultaneously biaxial stretch-formed method, biaxial stretch-formed method etc. successively, but from considerations such as planarity, dimensional stability, thickness deviations, preferably biaxial stretch-formed method successively.For example, use polyester film as time successively biaxial stretch-formed method, in the longitudinal direction more than 50 ℃ and below 110 ℃, roller is stretched to 1.6 times above and 4.0 times along its length, then, after tenter machine preheating, can be more than second-order transition temperature-40 of polyester ℃ and a second-order transition temperature+65 ℃ following broad ways stretch more than 1.2 times and below 5.0 times.And, can be after biaxial stretch-formed carry out heat fixation processing with the temperature below more than fusing point-40 of polyester ℃ and fusing point-10 ℃.
The base material film using in the present invention, for example, in order to give handlability (, the batching property after lamination), preferably makes to contain particle in film and forms projection on film surface.As the particle that makes to contain in film, can enumerate the inorganic particulates such as silicon-dioxide, kaolinite, talcum, calcium carbonate, zeolite, aluminum oxide, the thermotolerance polymer particles such as acrylic resin, PMMA, nylon, polystyrene, polyester, benzoguanamine-formaldehyde condensation products.From the viewpoint of transparent, the particle content in preferred film is few, for example, preferably more than 1ppm and below 1000ppm.And, from the viewpoint of transparent, preferably select the particle approaching with the specific refractory power of the resin using.In addition, in order to give as required film various functions, can make film contain photostabilizer (ultraviolet screener), pigment, antistatic agent etc.
Add man-hour in the surface enforcement printing that for example there is no lamination hard coat to hardcoat film for molding, total light penetration of preferred substrates film is more than 80%, and mist degree is below 5%.When the transparency of base material film is poor, the visibility while observing printed layers from hard coat side reduces.
The base material film using in the present invention, can be unitary film, 2 layers of above composite membrane of can be also lamination top layer and central core.The in the situation that of composite membrane, there is the function that can design independently top layer and central core.For example, the concavo-convex handlability that maintains can be formed by only making the top layer of thin thickness contain particle on surface, and the transparency of whole composite membrane can be further improved by making central core that thickness is thick in fact not contain particle.The manufacture method of above-mentioned composite membrane does not have special restriction, if but consider productivity, preferably by the raw material of top layer and central core is extruded by forcing machine separately, import in 1 mould and obtain, after drawing sheet, not making it at least carry out lamination at so-called coetrusion of single shaft direction orientation.
The thickness of the base material film using in the present invention is different and different according to material, but in the time using polyester film, more than lower limit is preferably 35 μ m, more preferably more than 50 μ m.On the other hand, the upper limit of thickness is preferably below 260 μ m, more preferably below 200 μ m.When thin thickness, not only handlability becomes bad, and heat to reduce the residual solvent of hard coat when dry time, easily produces heat wrinkle and planarity becomes bad on film.On the other hand, when thickness is thick,, easily there is the planarity that weavy grain (volume I addiction) causes bad in not only existing problems aspect cost, and in the time coiling into web-like and preserve.
(middle layer)
Hardcoat film for molding of the present invention, is the formation that lamination hard coat obtains on a surface of base material film, but preferably take the adaptation that improves base material film and hard coat as object, middle layer is set.And, make in film containing particle during in order to improve the transparency of base material film, by the time manufacturing film, the middle layer of containing particle is set simultaneously, can give base material film handlability.
As the resin that forms above-mentioned middle layer, can enumerate polyester resin, urethane resin, polyester urethane resin, acrylic resin, melamine resin and their hybrid resin etc., but in order to make that the adaptation of itself and base material film and hard coat is good and to select be important, particularly, if forming the resin of base material film and hard coat is acrylic acid or the like, preferably select at least a kind in acrylic acid or the like, copolyester class, polyester urethane class.
With the object that rises to of the raising of adaptation, water tolerance, also can make above-mentioned middle layer contain linking agent and form crosslinking structure.As linking agent, can enumerate urea class, epoxies, melamine class, isocyanates.And, also can not use linking agent, and be used as resin to there is the graft copolymer resin of self-crosslinking.
Improve slipperiness as object to make film surface form concavo-convex before hard coat forms, in middle layer, also can contain various particles.As the particle containing in middle layer, can enumerate the inorganic particulates such as such as silicon-dioxide, kaolinite, talcum, calcium carbonate, zeolite, aluminum oxide, the organic fillers such as acrylic resin, PMMA, nylon, vinylbenzene, polyester, benzoguanamine-formaldehyde condensation products.And, from the viewpoint of transparent, preferably select the particle approaching with the specific refractory power of the resin using.
As the method that middle layer is set, preferably coating method.As coating method, can use the known coating processes such as plate gravure coating method, kiss-coating mode, impregnation method, spraying method, showering mode, air knife blade coating mode, scraper plate coating method, reverse roll coating method, by the online coating method of coating layer being set in the manufacturing process of film, arranging manufacturing the off-line coating method that coating layer is set after film.In these modes, online coating method is not only good aspect cost, and by making middle layer contain particle, does not need to make base material film to contain particle, therefore can improve to heavens the transparency, thereby preferably.
(hard coat)
Hardcoat film for molding of the present invention, at least one surface of base material film directly or have hard coat across middle layer lamination.Hard coat in the present invention, represents to improve scuff resistance and have the tunicle higher than base material hardness and have the layer of the good formability of the distortion can follow moulding time in order to strengthen by the surface hardness of the film formed base material of base material.More specifically, hardcoat film for molding of the present invention, has surface hardness and is at least pencil hardness more than H, and have more than at least 10% elongation according to evaluation method described later, the label that can be preferred for such as household electrical appliances etc. with or building materials member etc.
Spendable hard coat in the present invention, must be take ionizing radiation gel-type resin as main component.Do not need as thermohardening type resin, when curing, to carry out heat treated, can reduce the thermal contraction of the base material film that heat causes, thereby preferably.Ionizing radiation curable compounds in the present invention, refers to by irradiating electron beam, radioactive rays, ultraviolet any one compound of polymerization and/or reaction occurs, this compound forms hard coat by there is polymerization and/or reaction.As the ionizing radiation curable compounds using in the present invention, can enumerate the ionizing radiation curable compounds of melamine class, acrylic acid or the like, silicon class, but wherein obtain preferred acrylate class ionizing radiation curable compounds aspect high surface hardness.
And the ionizing radiation curable compounds in the present invention, not only comprises monomer, precursor, certainly also comprise that their polymerization and/or reaction occur and the ionizing radiation gel-type resin that obtains.For example, as aforesaid propylene esters of gallic acid ionizing radiation curable compounds, there is no special restriction, can enumerate urethane acrylate, polyester acrylate, epoxy acrylate, polyalcohol acrylate etc., can use esters of acrylic acid ionizing radiation curable compounds arbitrarily.
Hard coat in the present invention, after the coating fluid that at least contains the ionizing radiation curable compounds of the functional group having more than 3 and the ionizing radiation curable compounds of 1 and/or 2 functional group is coated on base material film, there is polymerization and/or reaction by any one in irradiating electron beam, radioactive rays, ultraviolet ray, make thus it solidify.
In the time using esters of acrylic acid ionizing radiation curable compounds as ionizing radiation curable compounds; as the esters of acrylic acid ionizing radiation curable compounds of 1 functional group (simple function group) in the present invention, the compound that contains at least 1 (methyl) acryl as long as molecule does not have special system limit.For example, can enumerate acrylamide, (methyl) acryloyl morpholine, (methyl) vinylformic acid-7-amino-3,7-dimethyl monooctyl ester, isobutoxy methyl (methyl) acrylamide, (methyl) vinylformic acid isobornyl ethoxy ester, (methyl) isobornyl acrylate, (methyl) ethyl acrylate, (methyl) vinylformic acid ethyl binaryglycol ester, tertiary octyl group (methyl) acrylamide, diacetone (methyl) acrylamide, (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid lignocaine ethyl ester, (methyl) lauryl acrylate, (methyl) vinylformic acid Dicyclopentadiene (DCPD) ester, (methyl) vinylformic acid dicyclopentenyl ethoxy ester, (methyl) vinylformic acid two cyclopentenes esters, N, N-dimethyl (methyl) acrylamide tetrafluoro phenyl (methyl) acrylate, (methyl) vinylformic acid-2-tetra fluoro benzene 2-ethoxyethyl acetate, (methyl) vinylformic acid tetrahydro furfuryl ester, (methyl) tetrabromophenyl acrylate, (methyl) vinylformic acid-2-tetrabromo-benzene 2-ethoxyethyl acetate, (methyl) vinylformic acid-2-trichlorobenzene 2-ethoxyethyl acetate, (methyl) tribromophenyl acrylate, (methyl) vinylformic acid-2-tribromo-benzene 2-ethoxyethyl acetate, (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, caprolactam, NVP, N-vinyl formamide, (methyl) phenoxyethyl acrylate, (methyl) vinylformic acid fourth 2-ethoxyethyl acetate, (methyl) vinylformic acid pentafluorophenyl esters, (methyl) vinylformic acid pentabromo-phenyl ester, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, (methyl) vinylformic acid norbornene ester, methyl triglycol (methyl) acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid nonyl phenyl ester, and the derivative such as caprolactone modification thing, vinylformic acid etc. and their mixture etc.
In the time using esters of acrylic acid ionizing radiation curable compounds as ionizing radiation curable compounds, as the esters of acrylic acid ionizing radiation curable compounds of 2 functional groups in the present invention, can use this hydroxyl of the polyvalent alcohol in 1 molecule with more than 2 alcoholic extract hydroxyl group and the compound of 2 (methyl) acrylic acid carboxylates etc.Particularly, can enumerate: (a) (methyl) diester acrylates class of the alkylene glycol of carbonatoms 2～12: ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycol (methyl) acrylate etc.; (b) (methyl) acrylate acid diesters class of polyoxy alkylene glycol: Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate etc.; (c) (methyl) diester acrylates class of polyvalent alcohol: tetramethylolmethane two (methyl) acrylate etc.; (d) (methyl) diester acrylates class of the oxyethane of the hydride of dihydroxyphenyl propane or dihydroxyphenyl propane and propylene oxide adduct: 2,2 '-bis-(4-acyloxyethoxyphenyl) propane, 2,2 '-bis-(4-acyloxy propoxy-phenyl) propane etc.; (e) make polyisocyanate compound and react in advance and obtain containing terminal isocyanate group compound containing the compound of 2 above alcoholic extract hydroxyl groups, then making (methyl) acrylate reactions of itself and alcoholic hydroxy and in the molecule that obtains, there is carbamate type (methyl) esters of acrylic acid of 2 (methyl) acryloxies; (f) make to have in molecule the compound of more than 2 epoxy group(ing) and acrylic or methacrylic acid-respons and there is epoxy type (methyl) esters of acrylic acid of 2 (methyl) acryloxies etc. in the molecule that obtains.
In the time using esters of acrylic acid ionizing radiation curable compounds as ionizing radiation curable compounds, esters of acrylic acid ionizing radiation curable compounds as 3 in the present invention more than functional group, can enumerate: (a) particularly, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol three (methyl) acrylate, Dipentaerythritol four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, trimethylolpropane tris (methyl) acrylate etc., (b) polyisocyanate compound and the compound that contains more than 2 alcoholic extract hydroxyl group are reacted in advance obtain containing terminal isocyanate group compound, then make in its molecule obtaining with alcoholic hydroxy (methyl) acrylate reactions, to there are 3 carbamate type (methyl) esters of acrylic acids of (methyl) acryloxies above, (c) make to have in molecule the compound of more than 3 epoxy group(ing) and acrylic or methacrylic acid-respons and in the molecule that obtains, there is epoxy type (methyl) esters of acrylic acid etc. of 3 above (methyl) acryloxies.
In the present invention, in above-mentioned coating fluid in contained ionizing radiation curable compounds, it is important except the ionizing radiation curable compounds of 1 or 2 functional group, also containing a kind of above 3 more than functional group ionizing radiation curable compounds.In hard coat after solidifying, high 3 of cross-linking density ionizing radiation curable compounds composition more than functional group is as hard segment, they are reacted with the form of combination and the ionizing radiation curable compounds of 1 and/or 2 functional group, and the ionizing radiation curable compounds composition of 1 and/or 2 functional group exists as soft chain segment.By like this ionizing radiation curable compounds of more than two kinds different functional group's number being adjusted to specific concentration range, import different crosslinking structures to hard coat, can give surface hardness, scuff resistance by hard segment, and the retractility by soft chain segment is given formability, thereby can obtain the significant effect of the characteristic that has above-mentioned antinomy concurrently.
In the present invention, in order to have high surface hardness and good formability concurrently, to be particularly elongation more than pencil hardness and 10% more than H, the content of the ionizing radiation curable compounds of 1 and/or 2 functional group in above-mentioned coating fluid in contained ionizing radiation curable compounds is that the above and 95 quality % of 5 quality % are important below.When above-mentioned content is less than 5 quality %, the pliability of tunicle reduces, and on hard coat, cracks when moulding, therefore not preferred.In addition, when above-mentioned content exceedes 95 quality %, be difficult to obtain having the curing tunicle of sufficient surface hardness, scuff resistance.The lower limit of above-mentioned content more preferably 10 quality % above, more preferably more than 20 quality %.In addition, the upper limit of above-mentioned content more preferably 90 quality % following, more preferably 80 quality % following, be particularly preferably below 70 quality %.The content of the ionizing radiation curable compounds of 1 and/or 2 functional group in ionizing radiation curable compounds is more than 20 quality % and below 80 quality % time, can realize higher taking into account of surface strength and formability, particularly can have elongation more than pencil hardness and 20% more than 2H concurrently, the housing that is preferred for label use, the portable machine etc. of such as automobile etc. requires the molding film of high rigidity and high working property like that simultaneously.
And the inventor, except above-mentioned embodiment, also finds to have amino ionizing radiation curing compound as ionizing radiation curing compound by use, can take into account better surface hardness and formability., in preferred above-mentioned coating fluid, at least a kind of contained ionizing radiation curing compound has amino.There is about use the above-mentioned effect that amino compound brings as ionizing radiation curing compound, consider that its reason is as follows.In the time that hard coat exists part Hardness Distribution difference, in the time of stretching hard coat, easily there is local fracture (crackle).The reason of such part Hardness Distribution difference is, the polymerization (oxygen inhibition) of oxygen obstruction ionizing radiation cured resin.At this, use while having amino compound as ionizing radiation curing compound, amino Mulberry Extract oxygen, oxygen inhibition diminishes for the impact of the curing reaction of the skin section of hard coat, and there is uniform curing reaction in whole layer therefore.Thus, the stress dispersion that puts on hard coat when moulding is in whole layer, the generation of crackle can suppress moulding time.Therefore, can realize better and take into account surface elevation and formability.In addition, except above-mentioned effect, by making ionizing radiation cured resin contain amino, have the voltinism effect of tachy steroling of film, therefore solidifying compared with not when amino of hard coating surface, can promote curingly, and surface hardness can further improve.
The content that contains amino ionizing radiation curable compounds in above-mentioned coating fluid in contained ionizing radiation curable compounds, is preferably 2.5 quality % above and below 95 quality %.The lower limit of the content that contains amino ionizing radiation curable compounds in above-mentioned coating fluid in contained ionizing radiation curable compounds, more preferably more than 5 quality %, more preferably more than 10 quality %.In addition, the upper limit of above-mentioned content more preferably, below 92.5 quality %, more preferably, below 90 quality %, is particularly preferably below 50 quality %.When the content that contains amino ionizing radiation curable compounds in above-mentioned coating fluid in contained ionizing radiation curable compounds is less than 2.5 quality %, whole hard coat is difficult to solidify equably, the patience of the crackle while being difficult to obtain for moulding.In addition, when containing amino ionizing radiation curable compounds and being high density, the xanthochromia of the hard coat that amino causes strengthens, and when therefore above-mentioned content exceedes 95 quality %, damages sometimes high transparent.For example, implement printing add man-hour on surface to there is no lamination hard coat, the color b value of preferred film is below 2, now, above-mentionedly contains amino ionizing radiation curable compounds and is preferably below 92.5 quality %.
In above-mentioned coating fluid in the present invention, the ionizing radiation curable compounds that contains 1 and/or 2 functional group and there is the ionizing radiation curable compounds of 3 above functional groups, but in the above-described embodiment, as long as wherein the ionizing radiation curable compounds of a part contains amino.In addition, the ionizing radiation curable compounds of 1 functional group or the ionizing radiation curable compounds of 2 functional groups or to have any one in the ionizing radiation curable compounds of 3 above functional groups be to be preferred embodiment while containing amino ionizing radiation curable compounds.
Using esters of acrylic acid ionizing radiation curable compounds when thering is amino ionizing radiation curable compounds, for example, as thering is amino esters of acrylic acid ionizing radiation curable compounds, can enumerate acrylamide, (methyl) vinylformic acid-7-amino-3, 7-dimethyl monooctyl ester, isobutoxy methyl (methyl) acrylamide, tertiary octyl group (methyl) acrylamide, diacetone (methyl) acrylamide, (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid lignocaine ethyl ester, N, N-dimethyl (methyl) acrylamide tetrachloro phenyl (methyl) acrylate, N-vinyl formamide etc.
In addition, the inventor, except aforesaid way, also finds, by making hard coat contain particle, can further improve formability, and then can take into account better surface hardness and formability.About the effect that formability further improves by making hard coat contain particle, consider that its reason is as follows.When the hardness of hard coat increases, in the time of moulding, the hard coat that hardness is high produces strong stress for the moment, thereby hard coat quickly rupture (crackle).At this, by making there is particle in hard coat, the internal stress that puts on hard coat while making moulding relaxes at the interface of ionizing radiation curable compounds and particle, can suppress the generation of crackle, and there is on hard coat preferential generation without detriment to the effect of the visual small crackle that can not confirm of outward appearance degree, postponed hard coat fatal fracture occurs, result demonstrates the effect that moulding improves.
As the particle that hard coat is contained, for example can enumerate: soft silica, crystallinity silicon-dioxide, silica-alumina composite oxides, kaolinite, talcum, calcium carbonate (calcite type, vaterite-type), zeolite, aluminum oxide, the inorganic particulates such as hydroxyapatite, crosslink propylene acid particles, crosslinked PMMA particle, crosslinked polystyrene particle, nylon particle, polyester granules, benzoguanamine-formaldehyde condensation products particle, benzoguanamine-carbamide condenses particle, the thermotolerance polymer particles such as carbamide condenses particle, the organic/inorganic hybrid fine particles that silicon dioxide-acrylate complex chemical compound is such, but in the present invention, the kind of particle is not particularly limited.
As the shape of particle, can enumerate for example spherical, block, tabular, fibrous or sheet, but there is no special restriction, wherein, from the viewpoint of dispersed, the coming off of particle while contacting with other members, preferred spherical particle.
In the present invention, it is above and below 300nm that the median size of particle is preferably 10nm, be more preferably limited to down 40nm above, on be limited to below 200nm, be particularly preferably limited to down 50nm above, on be limited to below 100nm.The median size of particle is than 10nm hour, and median size is too small, and the raising effect of surface hardness that therefore above-mentioned interpolation particle brings, scuff resistance, formability all diminishes sometimes, or any one effect diminishes sometimes.In addition, when the median size of particle exceedes 300nm, hard coat tender, formability reduces sometimes.And above-mentioned median size is to use Ku Er counter (ベ ッ Network マ Application コ mono-Le タ mono-makes, マ Le チ サ ィ ザ mono-II type), particle is scattered in do not make the median size measured in its swelling solvent.
In the present invention, the content of the contained particle of hard coat, is preferably 5 quality % in solid composition in hard coat above and below 70 quality %, particularly preferably above-mentioned content under be limited to 15 quality % above, on be limited to below 50 quality %.The content of particle is than 5 quality % when few, and the raising effect of surface hardness that above-mentioned interpolation particle brings, scuff resistance, formability all diminishes sometimes, or any one effect diminishes sometimes.On the other hand, when the content of particle exceedes 70 quality %, small crackle above-mentioned when moulding produces in a large number, and mist degree rises (albefaction), the transparency of infringement formed body.
In addition, the inventor, except aforesaid way, also finds by making to contain ionizing radiation curing type silicone resin in hard coat, can give slipperiness, improves surperficial scuff resistance, take into account better table hardness and formability.Further, according to this method, an ionizing radiation-curable silicone resin itself due to the curing reaction of the crosslinking, and also according to the case of ionizing radiation curable resin is crosslinked and constituting the hard coating layer, thus forming a mold can be prevented in the silicone resin mold pollution caused by the long-term effects of the new molding obtained by molding a hard coat film of the present invention is molded by the surface of the abrasion resistance and the like of the function is not impaired.
Ionizing radiation curing type silicone resin, can enumerate free radical addition type, the hydrosilylation reactions type with thiazolinyl and hydrogen atom, the cationic polymerization type with epoxy group(ing) in molecule such as with thiazolinyl and sulfydryl, have the silicone resin of (methyl) acrylate-based radical polymerization mould assembly etc.Wherein, preferably have epoxy group(ing) cationic polymerization type, there is (methyl) acrylate-based radical polymerization mould assembly.
As thering is epoxy group(ing), (methyl) acrylate-based silicone resin in molecule, for example can enumerate: glycidoxy propyl group end-blocking polydimethylsiloxane, (epoxycyclohexyl ethyl) methylsiloxane-dimethylsiloxane copolymer, methacryloxypropyl end-blocking polydimethylsiloxane, acyloxy propyl group end-blocking polydimethylsiloxane etc.In addition, as the silicone resin in molecule with vinyl, can enumerate such as terminal ethylenyl groups polydimethylsiloxane, vinyl methylsiloxane homopolymer etc.
In the present invention, the addition of the contained ionizing radiation curing type silicone resin of hard coat, with respect to above-mentioned ionizing radiation curable compounds 100 mass parts for forming hard coat, preferably mix 0.15～15 mass parts, more preferably mix 0.3～13 mass parts, further preferably mix 0.5～5 mass parts.Under the combined amount deficiency of ionizing radiation curing type silicone resin, in limited time, the raising effect shortcoming of the scuff resistance while making formed body, in addition, exceedes in limited time, in the time that hard coat forms, sometimes solidifies and can not carry out fully.And the contained ionizing radiation curing type silicone resin of hard coat can use a kind, also can combine two or more use.
In the present invention, according to the purposes of molding film as above, preferably ionizing radiation curing compound is used and there is the situation of amino compound and add the suitable selection of situation of particle or combine in hard coat.As particularly preferred embodiment, situation is combined.Thus, can take into account admirably surface hardness and the formability of hard coat, particularly can obtain having surface hardness and be above and more than 20% elongation of 2H, more preferably there is the hardcoat film for molding that surface hardness is above and more than 30% elongation of 2H, can be preferred for cover member, the purposes such as housing, container at the dark end of such as automobile etc.
In the present invention, as the method that makes above-mentioned coating fluid generation polymerization and/or reaction, can enumerate irradiating electron beam, radioactive rays, ultraviolet method, but preferably in the time of irradiation ultraviolet radiation, in above-mentioned coating fluid, add Photoepolymerizationinitiater initiater.
As the object lesson of Photoepolymerizationinitiater initiater, can enumerate methyl phenyl ketone, 2, 2-diethoxy acetophenone, to dimethyl acetophenone, to dimethylamino Propiophenone, benzophenone, 2-chlorobenzophenone, 4, 4 '-dichloro benzophenone, 4, 4 '-bis-diethylin benzophenone, tetramethyldiaminobenzophenone, benzil, bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether, methyl benzoate, p-isopropyl-Alpha-hydroxy isobutyl phenyl ketone, Alpha-hydroxy isobutyl phenyl ketone, 2, 2-dimethoxy-2-phenyl methyl phenyl ketone, the carbonyl compound such as 1-hydroxycyclohexylphenylketone, tetramethylthiuram monosulfide, tetramethyl-thiuram disulfide, thioxanthone, CTX, the sulphur compounds such as 2-methyl thioxanthone, benzoyl peroxide, the superoxide such as ditertiary butyl peroxide.These Photoepolymerizationinitiater initiaters may be used alone, two or more kinds can also be used in combination.The addition of Photoepolymerizationinitiater initiater is preferably more than 0.01 mass parts and below 15 mass parts with respect to ionizing radiation curable compounds 100 mass parts contained in above-mentioned coating fluid, when usage quantity is few, reaction is slow, productivity is bad, and can not obtain sufficient surface hardness, scuff resistance due to residual unreacted reactant.Otherwise when addition is many, due to Photoepolymerizationinitiater initiater, hard coat produces the problem of xanthochromia.
In the present invention, Resorcinol, hydroquinone monomethyl ether, 2, the known thermopolymerization preventing agents such as 5-Tert. Butyl Hydroquinone are preferably added in the dark reaction in thermopolymerization, storage when preventing from manufacturing in above-mentioned coating fluid.The addition of thermopolymerization preventing agent is preferably more than 0.005 mass parts and below 0.05 mass parts with respect to ionizing radiation curable compounds 100 mass parts contained in above-mentioned coating fluid.
In the present invention, the workability when improving application, the control of application thickness is as object, can be not damaging in the scope of the object of the invention, and mixed organic solvents in above-mentioned coating fluid.
As organic solvent, the drying temperature while using low-melting material due to base material film after coating needs to be adjusted to below 150 ℃ sometimes, more than therefore preferably the boiling point of organic solvent is 50 ℃ and below 150 ℃.As concrete example, can enumerate the cyclic ether kind solvents such as the aromatic series such as ketones solvent, toluene kind solvent, dioxane such as acetate esters solvent, acetone, the methylethylketones such as the alcoholic solvents such as methyl alcohol, ethanol, Virahol, methyl acetate, ethyl acetate, butylacetate etc.These solvents can be separately or two or more mix and use.
In the present invention, take reduce coating fluid surface tension, improve that application outward appearance, the particularly micro-bubble of hard coat cause come off, foreign matter etc. adhere to crawling in depression, the drying process causing as object, can make to contain tensio-active agent in above-mentioned coating fluid.
That tensio-active agent preferably uses is cationic, the known tensio-active agent of anionic, non-ionic type, but due to rotten, the hard coat of above-mentioned coating fluid and the problem such as the adaptation of base material film is bad, preferably do not there is the non-ionic type of polar group, and then good organosilicone surfactants or the fluorochemical surfactant of the active ability of preferred surface.
As organosilicone surfactants, can enumerate dimethyl silscone, aminosilane, acrylate silane, the even acyloxy silane of vinyl benzene, PVC ニ Le ベ Application ジ シ Le ァ ミ ノ シ ラ Application, Racemic glycidol base silane, hydrosulphonyl silane, dimethylsilane, polydimethylsiloxane, polysiloxanes, hydrogenated diene modified siloxane, vinyl modified siloxanes, hydroxyl modification siloxanes, amino modified siloxanes, carboxy-modified siloxanes, halogenation modification siloxanes, epoxy-modified silicone oxygen alkane, methacryloxy modified siloxane, sulfhydryl modified siloxanes, fluorine modified siloxane, alkyl-modified siloxanes, phenyl modified siloxanes, oxirane modified siloxane etc.
As fluorochemical surfactant, can enumerate tetrafluoroethylene, perfluoroalkyl ammonium salt, perfluoroalkyl sulphonamide, perfluoro alkyl sulfonic acid sodium, perfluoroalkyl sylvite, perfluoroalkyl carboxylate, fluorinated alkyl sulfonate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl leptodactyline, the amino sulfonate of perfluoroalkyl, perfluoralkyl phosphate, perfluoroalkyl alkylate, perfluoroalkyl alkyl betaine, perfluoroalkyl halogenide etc.
From the viewpoint of improvement and the slipperiness of coating outward appearance, the content of tensio-active agent is preferably more than 0.01 quality % with respect to the coating fluid that forms hard coat.On the other hand, because tensio-active agent oozes out hard coating surface, pollutes the material that contacts hard coat, therefore the content of tensio-active agent is preferably below 2.00 quality %.
In addition, the tensio-active agent using, preferably HLB is more than 2 and below 12.Be more than 2 tensio-active agents by using HLB, can utilize surfactivity ability to improve levelling property (leveling).The HLB of tensio-active agent more preferably more than 3, is particularly preferably more than 4.On the other hand, be the tensio-active agent below 12 by using HLB, can suppress the variation of slipperiness.
In addition, HLB is the value of W.C.GriffiN called after Hydorophil Lyophile indexing BalaNce, using the balance of hydrophilic group contained in surfactant molecule and oleophilic group as characteristic value of the Atlas Powder company of the U.S..This HLB value is lower, represents that lipophilicity is higher, and on the other hand, HLB value is higher, represents that wetting ability is higher.
In hard coat of the present invention, can mix as required various additives.For example, can enumerate fluorine-containing, silicon compounds for hydrophobic property, for improving the defoamer of coating, outward appearance, and antistatic agent, the dyestuff of painted use, pigment.
In the present invention, hard coat is preferably by being applied to the coating fluid that contains ionizing radiation curable compounds, particle, Photoepolymerizationinitiater initiater, tensio-active agent in organic solvent on base material film and after dry, it being solidified to form.
As the method for lamination hard coat, can enumerate known method, preferably above-mentioned coating fluid is applied on base material film and is also dried afterwards, makes its curing method.As coating method, can enumerate the known coating processes such as plate gravure coating method, kiss-coating mode, impregnation method, spraying method, showering mode, air knife blade coating mode, scraper plate coating method, reverse roll coating method, excellent painting mode, lip coating method.In these, preferably can the application of volume to volume mode and the plate gravure coating method that can be coated with equably, the intaglio plate mode of particularly preferably reversing.
As the method that makes the contained ionizing radiation curable compounds of above-mentioned coating fluid, particle, Photoepolymerizationinitiater initiater etc. dissolve or disperse in organic solvent, preferably under heating, the method that stirred, disperse.By heating coating fluid, can improve the solvability of ionizing radiation curable compounds, particle and Photoepolymerizationinitiater initiater.Therefore, can suppress the variation of the application outward appearance that solute etc. does not cause.
Dispersion machine can use known dispersion machine.Particularly, can enumerate the Ga Behavior げ ら れ Ru such as ball mill, sand mill, masher, roller mill, agitator, colloidal mill, ultrasonic homogenizer, emulsifying homogeneous machine, micronizer (pearl mill), wet type aeropulverizer, oil plant bobbing machine (paint shaker), butterfly stirrer, planetary stirring machine, Henschel stirrer.
It is above and below 70 quality % that in above-mentioned coating fluid, the concentration of the solids component such as contained ionizing radiation curable compounds, particle, Photoepolymerizationinitiater initiater is preferably 5 quality %.More than the concentration of the solids component of coating fluid is adjusted to 5 quality %, can suppress to be coated with rear time of drying increases the decline of caused productivity.On the other hand, by the concentration of the solids component of coating fluid is adjusted to below 70 quality %, can prevent the variation of different caused levelling property variation in the viscosity of coating fluid and consequent coating outward appearance.In addition, from coating outward appearance aspect, preferably adjust the combined amount of the kind of the solid component concentration of coating fluid or the kind of organic solvent, tensio-active agent, so that in the scope of the viscosity of coating fluid more than 0.5cps and below 300cps.
The thickness of the hard coat after being coated with, solidifying, although the degree of the elongation while depending on moulding, preferably the thickness of the hard coat after moulding is more than 0.5 μ m and below 50 μ m.Particularly, more than the lower limit of the thickness of the hard coat before moulding is preferably 0.6 μ m, more preferably more than 1.0 μ m.In addition, the upper limit of the thickness of the hard coat before moulding be preferably 100 μ m following, more preferably 80 μ m following, more preferably 60 μ m following, particularly preferably below 20 μ m.The Thickness Ratio 0.6 μ m of hard coat when thin, is difficult to obtain painting property firmly, otherwise, while exceeding 100 μ m, demonstrate the tendency of curing bad, the curling difference that cure shrinkage is brought of hard coat.
In coating fluid, mix in the situation etc., the pre-dry situation of needs of organic solvent, as being coated with and carrying out dry method, can enumerate known warm air drying, infrared heating etc. on base material film, but the preferred fast warm air drying of rate of drying.
Preferably the drying temperature after coating is to carry out under the condition more than 40 ℃ and below 120 ℃, be particularly preferably limited to down 45 ℃ above, on be limited to below 80 ℃.When lower than 40 ℃, the contained organic solvent of coating fluid can not be removed fully, and sometimes produces the problems such as brush mark.Otherwise, in the time that temperature exceedes 120 ℃, easily producing from the small defect of the small coating shedding of bubble, the small film such as crawling, crackle, outward appearance becomes bad sometimes.And film shrinks strongly because of heat, because of the planarity variation of heat wrinkle film, therefore can not extend equably when moulding, or local elongation occurs, there is film fracture etc., it is bad that formability becomes.
The tension force of the film in dry is preferably that 50N/m is above and 300N/m is following, be particularly preferably limited to down 100N/m above, on be limited to below 250N/m.When the tension force of film is less than 50N/m, the film moving ahead crawls, can not application coating fluid.Otherwise, while exceeding 300N/m, on film, produce fold, the degraded appearance of planarity variation, the film that batches.And, be the good film of low temperature compacted under at base material film, in being dried, to shrink along the stretching of Mo Jin line direction, width, the poorest situation is fracture etc. to occur aspect productivity, have problems.
In the present invention, not hindering in the scope of effect of the present invention, also can give hard coat, charged preventing layer, easily adhesive linkage, bonding coat, slippery layer, electromagnetic wave absorbing layer, other functions such as resin layer of containing the pigment such as dyestuff or pigment to the surface of hard coat is not set.
In the present invention, by coating fluid irradiation ultraviolet radiation is formed to hard coat.As the accumulated light irradiating, preferably 50mJ/cm 2above and 1000mJ/cm 2below, be more preferably limited to down 300mJ/cm 2above,, be limited to 700mJ/cm 2below.In addition, when irradiation, preferably under nitrogen atmosphere, carry out, because can reduce oxygen inhibition, raising scuff resistance.Accumulated light is less than 50mJ/cm 2time, the polyreaction of ionizing radiation curable compounds can not get promotion, and the surface hardness of hard coat significantly reduces.Accumulated light exceedes 1000mJ/cm 2time, exist base material film to be influenced by heat and the situation of being out of shape.In addition, the accumulated light in the present invention can be measured by ト プ コ Application system " UVR-T35 ".
And in the time utilizing electron beam that coating fluid is solidified, illuminated line amount is preferably that 5kGy is above and 100kGy following, be limited on particularly preferably 30kGy take upper and lower limit below 70kGy.In the time being less than 5kGy, the polyreaction of ionizing radiation curable compounds can not get promotion, and the surface hardness of hard coat significantly reduces.In the time exceeding 100kGy, the life-span of electron beam irradiation tube reduces significantly, also not preferred aspect production cost.
(hardcoat film for molding)
Hardcoat film for molding of the present invention is the film that surface hardness is good.Particularly, according to the difference of base material film and different, but in the situation of hardcoat film for molding using the double axial orientated polyester film that contains copolyester as base material film, the measured value of pencil hardness be H when above preferably so that for 2H when above particularly preferably.At this, the evaluation of pencil hardness is carried out according to JIS-K5600.
As the method for adjustment sheet surface hardness, can be by forming the amount of particle in the content, the content with amino ionizing radiation curable compounds, hard coat of ionizing radiation curable compounds of 1 or 2 functional group in the contained ionizing radiation curable compounds of the coating fluid of hard coat, the thickness of hard coat changes.
Hardcoat film for molding of the present invention is the film that scuff resistance is good.Particularly, different and different according to base material film, but in the case of the hardcoat film for molding using the double axial orientated polyester film that contains copolyester as base material film, according to JIS-K5600, use #0000 steel wool with load 500gf on surface reciprocal 20 times, visual observation has or not the degree of scar generation and scar, dark scar is few preferred to time below 10, so while thering is no dark scar completely particularly preferably.
As adjusting the method for scuff resistance, can change by the amount that forms particle in the content, the content with amino ionizing radiation curable compounds, hard coat of ionizing radiation curable compounds of 1 or 2 functional group in the contained ionizing radiation curable compounds of the coating fluid of hard coat.
Hardcoat film for molding of the present invention is the film that formability is good.Particularly, different and different according to base material film, but in the case of the hardcoat film for molding using the double axial orientated polyester film that contains copolyester as base material film, in the time that room temperature, film actual temperature are 160 ℃, elongation be 10% when above preferably, be more than 20% more preferably, be more than 30% particularly preferably.At this, elongation refer to by hardcoat film for molding be cut into the strip of long 10mm, wide 150mm, while stretching respectively in the time that film actual temperature is 160 ℃, on hard coat, crack or extensibility when albefaction, set it as elongation (%).
As the method for adjusting formability (elongation), can change by the amount that forms particle in the content, the content with amino ionizing radiation curable compounds, hard coat of ionizing radiation curable compounds of 1 or 2 functional group in the contained ionizing radiation curable compounds of the coating fluid of hard coat.
Hardcoat film for molding of the present invention, implements printing on the surface to there is no lamination hard coat and adds man-hour, preferably has the transparency.Particularly, different and different according to base material film, but in the case of the hardcoat film for molding using the double axial orientated polyester film that contains copolyester as base material film, mist degree is preferred below 5% time.As the method for adjusting mist degree, can change according to the amount of particle in hard coat.
Hardcoat film for molding of the present invention, implements printing on the surface to there is no lamination hard coat and adds man-hour, preferably not painted.Particularly, different and different according to base material film, but in the case of the hardcoat film for molding using the double axial orientated polyester film that contains copolyester as base material film, tone b *value be preferred below 2.0 time.As adjusting tone b *method, can be by forming the content with amino ionizing radiation curable compounds in the contained ionizing radiation curable compounds of the coating fluid of hard coat, the addition of Photoepolymerizationinitiater initiater changes.At this, tone b *the visual angles mensuration tone b that uses colour-difference meter (Japanese electric look industry system, ZE-2000), spends with illuminant-C, 2 *value is also averaged the measured value of 5 times and the value obtained.
(hardcoat film for molding volume)
Hardcoat film for molding volume of the present invention, through coiling into long hardcoat film for molding the operation of web-like continuously and obtain in cylinder formed core.By using hardcoat film for molding volume, the productivity that adds man-hour improves, and can contribute to the stability of the quality of formed body.The length that long hardcoat film for molding is coiled into continuously in cylinder formed core to the hardcoat film for molding volume that web-like forms, does not have special restriction according to purposes yet, but preferably 50m is above and below 5000m, and more preferably 100m is above and below 3000m.Volume length in short-term, for example after printed layers in operation add man-hour, the replacement frequency of hardcoat film for molding increases, workability variation.Otherwise when volume length is long, hardcoat film for molding, along with outside envrionment temperature expands and shrinks, batches tension, the outward appearance of volume core becomes bad.
The width of hardcoat film for molding volume is according to purposes difference and different, and there is no particular limitation, but from processibility aspect, preferably more than 100mm and below 2000mm, more preferably more than 500mm and below 1500mm.
The preferred plastics coremaking of cylinder formed core of hard coat film for coiling and molding.Using when normally used core made of paper, produce paper powder etc. and be attached on hard coat and easily become bad.As plastics coremaking, can preferably use known core, but from the viewpoint of intensity, optimization polypropylene coremaking or FRP coremaking.More than the gravel size decision diameter of cylinder formed core is 3 inches and below 6 inches.While using the little core of diameter, on volume core with weavy grain, after operability in operation become bad.On the other hand, when diameter is large, coil diameter increases, and it is bad that handlability becomes.
For coiling and molding hard coat film on core, start to batch after preferably hardcoat film for molding being fixed on core by double sticky tape.While not using double sticky tape, in the time batching midway, carry, easily there is volume skew.As double sticky tape, can use known double sticky tape, but from the viewpoint of generation and the intensity of paper powder, preferably two surfaces of plastic film has the double sticky tape of bonding coat.More than the thickness of double sticky tape is preferably 5 μ m and below 50 μ m.The bed knife of strength decreased when thin and workability variation and film reduces.Otherwise adhesive tape exists thickness difference when thick, the planarity of the hardcoat film for molding of volume core becomes bad.
In the present invention, preferably give the width two ends concavo-convex (stamp) of hardcoat film for molding.Concavo-convex by giving, be not easy to take volume core to from the vestige of double sticky tape, and hard coat and on the base material film top layer of its opposing face or base material film the contact part of the layer of having given above-mentioned functions of lamination reduce, it is good that the storage stability of scroll state becomes.The lower limit of concavo-convex height is preferably 10 μ m, 15 μ m more preferably.On the other hand, the upper limit of concavo-convex height is preferably 40 μ m, 35 μ m more preferably.When concavo-convex height is too low, the effect of improving of the storage stability of the concavo-convex scroll state of bringing diminishes.On the other hand, when concavo-convex excessive height, when transportation, easily there is volume skew etc.As giving concavo-convex method, can use known method.Particularly, can enumerate and bossed tool metallic roll is pressed to surface and give concavo-convex method.And, before preferably forming hard coat on base material film, in advance base material film is implemented to concavo-convex processing.
(formed body)
Hardcoat film for molding of the present invention preferably as by vacuum forming, press the molding material of the forming method moulding such as empty moulding, mould molding, impact briquetting, laminated into type, injection moulding, drawing and forming, brake forming, drawing and forming.In the time using hardcoat film for molding moulding of the present invention, distortion when hard coat is not followed moulding cracks, and can maintain surface hardness, scuff resistance.
The thickness of the hard coat of the formed body that above-mentioned hardcoat film for molding moulding is formed, more than being preferably 0.5 μ m and below 50 μ m, more than being particularly preferably 0.5 μ m and below 10 μ m.The Thickness Ratio 0.5 μ m of the hard coat of formed body when thin, can not obtain painting property firmly, and aspect thermotolerance, when formed body is heated, hard coating surface can not be followed the contraction of base material film, but rises and falls into fold, impairs outward appearance.Otherwise when the thickness of the hard coat of formed body exceedes 50 μ m, the thickness of hard coat is at this more than thickness, surface hardness does not have good and bad difference, and the advantage aspect quality diminishes.
As above the formed body of moulding, strengthen surface hardness by thering is hard coat, therefore can be preferably as being arranged on and the shaped component use such as label, vapour mobile-used signs, emulation tank, building materials, change make-up plate, decorative steel plate, the transfer sheet household electrical appliances for position, that require scuff resistance of external contact.
Embodiment
Below by embodiment, the present invention is at length described.In addition, the membrane property obtaining by each embodiment is measured, is evaluated by following method.
(1) elongation
Cut out the bar-shaped sample sheet of long 10mm, wide 150mm from the hardcoat film for molding of gained.Be that under the environment of 160 ℃, visual observation outward appearance, holds film two ends simultaneously and stretch with trial speed 250mm/ minute in the actual temperature of film coupons, measure and on hard coat, crack or the length of film when albefaction.
Film coupons length before test is designated as to film coupons length after a, test while being designated as b, calculates elongation by following formula.
Elongation (%)=(b-a) × 100/a
At this, elongation is 10% when above, is judged as formability good, and elongation is 30% when above, is judged as formability good especially.
(2) pencil hardness
Measure the pencil hardness of the hard coat of the hardcoat film for molding of gained according to JIS-K5600.Visual judgement impression.
At this, pencil hardness is H when above, is judged as and has good surface hardness, and pencil hardness is 2H when above, is judged as and has good especially surface hardness.
(3) scuff resistance
Measure the scuff resistance of the hard coat of the hardcoat film for molding of gained according to JIS-K5600.With the steel wool of #0000, with the load of 500gf at hard coating surface reciprocal 20 times, visual observation has or not scar to produce and the degree of scar.Based on observations, judge grade according to following judging criterion.The grade of this scuff resistance is C when above, is judged as and has scuff resistance, and the grade of scuff resistance is B when above, is judged as scuff resistance good.
A: do not produce scar or observe the tiny scar of a small amount of degree.
B: observe tiny scar, but do not observe dark scar.
C: observe tiny scar, also observe the dark scar of a small amount of degree.
D: observe a large amount of dark scars.
(4) tone b *
Use colour-difference meter (Japanese electric look industry system, ZE-2000), measure tone b with the visual angle of illuminant-C, 2 degree *value, is averaged the measured value of 5 times, obtains the tone b of the hardcoat film for molding of gained *value.
(5) thickness of the pencil hardness after moulding, hard coat
In the evaluation of the elongation of above-mentioned (1), stretch by stopping before just will cracking, obtain the formed body after drawing and forming.Pencil hardness after moulding is evaluated by the evaluation method of above-mentioned (2).In addition, the spectral reflectance at the central part place of the film coupons (formed body) after moulding utilizes spectrophotometer (Shimadzu Seisakusho Ltd.'s system, UV-3150 type) to obtain, and is calculated the thickness of hard coat by the waveform more than wavelength 400nm and below 600nm, use peak valley method.The now specific refractory power of required hard coat, is used Abbérefractometer (ァ タ go system, NAR-1T SOLID) to obtain to the monofilm of being made hard coat by the hard painting coating fluid of each embodiment, comparative example.
(6) there is corrugationless to produce
Whether suitable in order to judge drying temperature, film tension force after coating coating fluid, evaluate corrugationless and produced.On the base material film of wide 1000mm, long 200m, coating is solidified and when hard coat is set, and the hardcoat film for molding of gained is judged as good (zero) while not producing fold, be judged as bad (×) while producing fold.
(7) application outward appearance
Whether suitable in order to judge drying temperature, film tension force after coating coating fluid, evaluate application outward appearance.On the base material film of wide 1000mm, long 200m, coating is solidified and when hard coat is set, is judged as good (zero) on hard coat while not finding brush mark (brushing), coating shedding, crawling completely, is judged as bad (×) while finding defect.
(8) the width shrinking percentage before and after application
Whether suitable in order to judge drying temperature, film tension force after coating coating fluid, evaluate width shrinking percentage.On the base material film of wide 1000mm, long 200m, coating is solidified and is arranged after hard coat, measures film width.When film width before application is designated as to film width after a, application and is designated as b, obtained the shrinking percentage (width shrinking percentage) of the film width before and after application by following formula.Width shrinking percentage be judged as below 1.5% time good, be judged as while exceeding 1.5% bad.
Width shrinking percentage (%)=(a-b) × 100/a
(embodiment 1)
There is the double axial orientated polyester film that contains copolyester (Japan's weaving system of easy adhesive linkage on two surfaces, ソ Off ト シ ャ ィ Application: A1532, thickness 125 μ m) on, use ring rod to be coated with following coating fluid A, making the thickness of the hard coat after coating is solidified is 2 μ m, in the hot blast of 80 ℃ of temperature, be dried 60 seconds, position (the accumulated light 300mJ/cm of 20cm under the high pressure mercury vapour lamp of output 120W/cm 2) speed sentenced 8m/ minute passes through, and obtains hardcoat film for molding.
(coating fluid A)
Following material is mixed with the mass ratio shown in following, stir 30 points and make above its dissolving.Then, use nominal filter fineness is that the strainer of 1 μ m is removed not solute, makes coating fluid A.
Methylethylketone 64.48 quality %
Pentaerythritol triacrylate 11.45 quality %
(Xin Zhong village chemistry system, NK ェ ス Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 5.73 quality %
(Xin Zhong village chemistry system, NK ェ ス Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 5.72 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 11.45 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 2)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid B, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid B)
Methylethylketone 64.48 quality %
Pentaerythritol triacrylate 17.18 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 2.86 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 2.86 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 11.45 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 3)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid C, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid C)
Methylethylketone 64.48 quality %
Pentaerythritol triacrylate 8.02 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 7.44 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 7.44 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 11.45 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 4)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid D, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid D)
Methylethylketone 64.48 quality %
Pentaerythritol triacrylate 21.75 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 0.58 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 0.57 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 11.45 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 5)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid E, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid E)
Methylethylketone 64.48 quality %
Pentaerythritol triacrylate 1.15 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 0.58 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 21.17 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 11.45 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 6)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid F, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid F)
Methylethylketone 64.48 quality %
Pentaerythritol triacrylate 21.75 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 1.15 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Silicon dioxide microparticle 11.45 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 7)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid G, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid G)
Methylethylketone 64.48 quality %
Pentaerythritol triacrylate 1.15 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 21.75 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Silicon dioxide microparticle 11.45 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 8)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid H, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid H)
Methylethylketone 64.48 quality %
Pentaerythritol triacrylate 1.15 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 21.75 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 11.45 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
Obtain the vertical good ま of the Chi ゃ ゃ く な い Ga formability of the painted Ga order of ら れ hardcoat film for molding は ァ ミ Application compound addition Ga many い め, surface hardness, the good In あ of scuff resistance は と も To つ.ま, the good In あ of ら れ hardcoat film for molding ょ り moulding formed body surface hardness も つ.Obtain ら れ result The table 1 To and show The.
(embodiment 9)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid I,
Operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid I)
Methylethylketone 64.48 quality %
Pentaerythritol triacrylate 11.45 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 5.73 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Diethylaminoethyl methacrylate 5.72 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DE, functional group's number 1 altogether)
Silicon dioxide microparticle 11.45 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 10)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid J, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid J)
Methylethylketone 64.48 quality %
Pentaerythritol triacrylate 11.45 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 5.73 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
N-vinyl formamide 5.72 quality %
(waste river chemistry system, PVC one system セ ッ ト 770, functional group's number 1)
Silicon dioxide microparticle 11.45 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 11)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid K, operation, obtains hardcoat film for molding similarly to Example 1.
(being firmly coated with coating fluid K)
Methylethylketone 67.93 quality %
Pentaerythritol triacrylate 11.58 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 5.79 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 5.79 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 7.72 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 1.16 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 12)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid L, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid L)
Methylethylketone 4.24 quality %
Pentaerythritol triacrylate 6.22 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 3.12 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 3.12 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 82.73 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 0.55 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.02 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 13)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid M, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid M)
Methylethylketone 71.46 quality %
Pentaerythritol triacrylate 11.72 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 5.86 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 5.86 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 3.90 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 1.17 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 14)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid N, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid N)
Pentaerythritol triacrylate 5.28 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 2.64 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 2.64 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 88.88 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 0.55 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.02 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 15)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid O, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid O)
Methylethylketone 58.76 quality %
Pentaerythritol triacrylate 11.45 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 5.73 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 5.72 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 17.17 quality %
(Japan's chemical industry system, PL2L-MEK, solids component ratio: 20%, median size: 20nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 16)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid P, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid P)
Methylethylketone 58.76 quality %
Pentaerythritol triacrylate 11.45 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 5.73 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 5.72 quality %
(Sakae society chemistry system, ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 17.17 quality %
(Japan's chemical industry system, PL30L-MEK, solids component ratio: 20%, median size: 297nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 17)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid Q, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid Q)
Methylethylketone 58.76 quality %
Pentaerythritol triacrylate 11.45 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 5.73 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 5.72 quality %
(Sakae society chemistry system, テ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 17.17 quality %
(Japanese catalyst system, シ mono-ホ ス タ mono-KE-E50, solids component ratio: 20%, median size: 511nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 18)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid R, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid R)
Methylethylketone 72.50 quality %
Pentaerythritol triacrylate 11.45 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 5.73 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 5.72 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Carbamide condenses particulate 3.43 quality %
(Japanese catalyst system, ェ Port ス タ mono-S, median size: 196nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 19)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid S, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid S)
Methylethylketone 75.08 quality %
Pentaerythritol triacrylate 11.85 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 5.93 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 5.92 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Photoepolymerizationinitiater initiater 1.19 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 20)
Have the biaxially oriented polyester film of easy adhesive linkage (Japan weaving コ ス モ シ ャ ィ Application processed: A4300, thickness 125 μ m) in addition, operate similarly to Example 1, obtain hardcoat film for molding except the base material film in embodiment 1 being changed to two surfaces.
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 21)
Except the base material film in embodiment 1 is changed to the polycarbonate membrane that do not stretch, (Supreme Being people changes into system, PC-2151, thickness 250 μ m) and by the coating fluid that forms hard coat change to beyond following coating fluid T, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid T)
Methylethylketone 20.98 quality %
Virahol 40.50 quality %
Pentaerythritol triacrylate 11.45 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 5.73 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 5.72 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 11.45 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 22)
Making in embodiment 1 thickness of the hard coat after coating is solidified except being coated with is 1.1 μ m, and operation, obtains hardcoat film for molding similarly to Example 1.
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 23)
Making in embodiment 1 thickness of the hard coat after coating is solidified except being coated with is 50 μ m, and operation, obtains hardcoat film for molding similarly to Example 1.
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 24)
Making in embodiment 1 thickness of the hard coat after coating is solidified except being coated with is 0.5 μ m, and operation, obtains hardcoat film for molding similarly to Example 1.
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.But, slightly bad by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.This is because by moulding, the thickness attenuation of hard coat, and be able to maintain beyond the scope of surface hardness.By the table 1 that the results are shown in of gained.
(embodiment 25)
Making in embodiment 1 thickness of the hard coat after coating is solidified except being coated with is 60 μ m, and operation, obtains hardcoat film for molding similarly to Example 1.
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(comparative example 1)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid U, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid U)
Methylethylketone 64.48 quality %
Pentaerythritol triacrylate 22.90 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Silicon dioxide microparticle 11.45 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ リ テ ィ mono-ィ Le ガ キ ュ ァ 184 processed)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The surface hardness of the hardcoat film for molding of gained, scuff resistance, coloring degree are all good, but formability is bad, bad as hardcoat film for molding.By the table 1 that the results are shown in of gained.
(comparative example 2)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid V, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid V)
Methylethylketone 64.48 quality %
Tri (propylene glycol) diacrylate 11.45 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 11.45 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 11.45 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ リ テ ィ mono-ィ Le ガ キ ュ ァ 184 processed)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
Formability, the coloring degree of the hardcoat film for molding of gained are all good, but surface hardness, scuff resistance are bad, bad as hardcoat film for molding.By the table 1 that the results are shown in of gained.
(embodiment 26)
Two surfaces are there is to the double axial orientated polyester film that contains copolyester (Japan's weaving system, the ソ Off ト シ ャ ィ Application: the film of A1532, thickness 125 μ wide 1000mm, long 200m m) is rolled up, under volume to volume, used nick version mode to be coated with following coating fluid W of easy adhesive linkage, making the thickness of the hard coat after coating is solidified is 2 μ m, under the condition of film tension force 180N/m, with the warm air drying of 80 ℃ of temperature 60 seconds, position (the accumulated light 300mJ/cm of 20cm under the high pressure mercury vapour lamp of output 160W/cm 2) sentence the speed of 10m/ minute by it is solidified, then hardcoat film for molding is rolled onto in the cylinder formed core of 6 inches of diameters of polypropylene system, make the hardcoat film for molding of wide 1000mm, long 200m and roll up.
(coating fluid W)
Following material is mixed with the mass ratio shown in following, stir 30 points and make above its dissolving.Then, use nominal filter fineness is that the strainer of 1 μ m is removed not solute, makes coating fluid U.
Methylethylketone 28.24 quality %
Toluene 36.24 quality %
Pentaerythritol triacrylate 11.45 quality %
(Xin Zhong village chemistry system, NK ェ ス Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 5.73 quality %
(Xin Zhong village chemistry system, NK ェ ス Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 5.72 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 11.45 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
On base material film, coating is solidified when hard coat, and the film that can make to move ahead does not produce and crawls, fold and productivity are made no problemly.The application outward appearance of the hardcoat film for molding of gained is good, and width shrinking percentage is also good.In addition, the hardcoat film for molding of gained has the formability equal with embodiment 1, surface hardness, scuff resistance, and the surface hardness of its formed body is also good.By the table 2 that the results are shown in of gained.
(embodiment 27)
Except the drying temperature in embodiment 26 is changed to 40 ℃, operation similarly to Example 26, makes hardcoat film for molding volume.
On base material film, coating is solidified when hard coat, and the film that can make to move ahead does not produce and crawls, fold and productivity are made no problemly.The application outward appearance of the hardcoat film for molding of gained is good, and width shrinking percentage is also good.In addition, the hardcoat film for molding of gained has the formability equal with embodiment 1, surface hardness, scuff resistance, and the surface hardness of its formed body is also good.By the table 2 that the results are shown in of gained.
(embodiment 28)
Except the drying temperature in embodiment 26 is changed to 120 ℃, operation similarly to Example 26, makes hardcoat film for molding volume.
On base material film, coating is solidified when hard coat, and the film that can make to move ahead does not produce and crawls, fold and productivity are made no problemly.The application outward appearance of the hardcoat film for molding of gained is good, and width shrinking percentage is also good.In addition, the hardcoat film for molding of gained has the formability equal with embodiment 1, surface hardness, scuff resistance, and the surface hardness of its formed body is also good.By the table 2 that the results are shown in of gained.
(embodiment 29)
Except the film tension force in embodiment 26 is changed to 50N/m, operation similarly to Example 26, makes hardcoat film for molding volume.
On base material film, coating is solidified when hard coat, and the film that can make to move ahead does not produce and crawls, fold and productivity are made no problemly.The application outward appearance of the hardcoat film for molding of gained is good, and width shrinking percentage is also good.In addition, the hardcoat film for molding of gained has the formability equal with embodiment 1, surface hardness, scuff resistance, and the surface hardness of its formed body is also good.By the table 2 that the results are shown in of gained.
(embodiment 30)
Except the film tension force in embodiment 26 is changed to 300N/m, operation similarly to Example 26, makes hardcoat film for molding volume.
On base material film, coating is solidified when hard coat, and the film that can make to move ahead does not produce and crawls, fold and productivity are made no problemly.The application outward appearance of the hardcoat film for molding of gained is good, and width shrinking percentage is also good.In addition, the hardcoat film for molding of gained has the formability equal with embodiment 1, surface hardness, scuff resistance, and the surface hardness of its formed body is also good.By the table 2 that the results are shown in of gained.
(comparative example 3)
Except the drying temperature in embodiment 26 is changed to 30 ℃, operation similarly to Example 26, makes hardcoat film for molding volume.
On base material film, coating is solidified when hard coat, and the film that can make to move ahead does not produce and crawls, fold and productivity are made no problemly.The width shrinking percentage of the hardcoat film for molding of gained is also good, bad but application outward appearance produces brush mark.By the table 2 that the results are shown in of gained.
(comparative example 4)
Except the drying temperature in embodiment 26 is changed to 140 ℃, operation similarly to Example 26, makes hardcoat film for molding volume.
When hard coat is solidified in coating on base material film, although the film moving ahead does not crawl, produced fold, productivity is not good yet.The application outward appearance of the hardcoat film for molding of gained finds that small coating shedding, crawling are and bad, and width shrinking percentage is also bad.By the table 2 that the results are shown in of gained.
(comparative example 5)
Except the film tension force in embodiment 26 is changed to 40N/m, operation similarly to Example 26, makes hardcoat film for molding volume.
When on base material film, hard coat is solidified in coating, although do not produce fold, the film moving ahead crawls, and productivity is not good.Due to crawling of this film moving ahead, can not make hardcoat film for molding.
(comparative example 6)
Except the film tension force in embodiment 26 is changed to 320N/m, operation similarly to Example 26, makes hardcoat film for molding volume.
When hard coat is solidified in coating on base material film, although the film moving ahead does not crawl, produced fold, productivity is not good.The application outward appearance of the hardcoat film for molding of gained is good, but width shrinking percentage is bad.By the table 2 that the results are shown in of gained.
(embodiment 31)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid R, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid X)
Methylethylketone 63.62 quality %
Pentaerythritol triacrylate 11.45 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 5.73 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 5.72 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 11.45 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Ionizing radiation curing type silicone compound polyether acrylate 0.86 quality %
(De ィ ッ ケ ミ mono-サ mono-PVC ス company system, TEGO Rad2200N)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 32)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid Y, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid Y)
Methylethylketone 64.42 quality %
Pentaerythritol triacrylate 11.45 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 5.73 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 5.72 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 11.45 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Ionizing radiation curing type silicone compound polyether acrylate 0.06 quality %
(De ィ ッ ケ ミ mono-サ mono-PVC ス company system, TEGO Rad2200N)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The formability of the hardcoat film for molding of gained, surface hardness, scuff resistance, coloring degree are all good, good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
(embodiment 33)
Except the coating fluid that forms hard coat in embodiment 1 is changed to following coating fluid Z, operation, obtains hardcoat film for molding similarly to Example 1.
(coating fluid Z)
Methylethylketone 61.62 quality %
Pentaerythritol triacrylate 11.45 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le A-TMM-3LM-N, functional group's number 3)
Tri (propylene glycol) diacrylate 5.73 quality %
(Xin Zhong village chemistry system, NK ェ ス テ Le APG-200, functional group's number 2)
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 5.72 quality %
(Sakae society chemistry system, ラ ィ ト ェ ス テ Le DM, functional group's number 1 altogether)
Silicon dioxide microparticle 11.45 quality %
(daily output chemical industry system, MEK-ST-L, solids component ratio: 30%, median size: 50nm)
Ionizing radiation curing type silicone compound polyether acrylate 2.86 quality %
(De ィ Star ケ ミ mono-サ mono-PVC ス company system, TEGO Rad2200N)
Photoepolymerizationinitiater initiater 1.14 quality %
(チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ ィ Le processed ガ キ ュ ァ 184)
Organosilicone surfactants 0.03 quality %
(East レ ダ ゥ コ mono-ニ Application グ system, DC57)
The hardcoat film for molding formability of gained, surface hardness, scuff resistance, coloring degree are all good, and good as hardcoat film for molding.In addition, also good by the surface hardness of the formed body of the hardcoat film for molding moulding of gained.By the table 1 that the results are shown in of gained.
Table 1
Figure BPA00001278441300521
Table 2
Table 3
Figure BPA00001278441300531
Utilizability in industry
Hardcoat film for molding of the present invention is owing to having hard coat and strengthened the surface hardness of base material film, therefore formed body hardcoat film for molding moulding of the present invention being formed, the label that is suitable as the household electrical appliances, the automobile that require scuff resistance with or the housing of portable machine, the notebook PC etc. such as member, mobile phone, sound equipment, portable player/sound-track engraving apparatus, IC sound-track engraving apparatus, automobile navigation apparatus, PDA for building materials.In addition, at the manufacture view of forming process, by processing hard coat and be laminated on base material film before moulding, can contribute to boost productivity, the stability of quality, very large to the contribution of industrial community.

Claims (5)

1. a hardcoat film for molding, its have at least one surface of base material film, be coated with coating fluid and make its solidify hard coat of forming and as by being selected from vacuum forming, press empty moulding, the molding material of forming method moulding in mould molding, impact briquetting, laminated into type, injection moulding, drawing and forming, brake forming, drawing and forming
Described base material film is the double axial orientated polyester film that contains copolyester,
Described copolyester is by aromatic dicarboxylic acid composition and contains ethylene glycol and copolyester that the diol component of chain aliphatic diol or alicyclic diol forms or the copolyester that is made up of the aromatic dicarboxylic acid composition that contains terephthalic acid and m-phthalic acid and the diol component that contains ethylene glycol
Described coating fluid at least contain there is 3 above ionizing radiation curable compounds of functional group and the ionizing radiation curable compounds of 1 and 2 functional group,
The content of the ionizing radiation curable compounds of 1 and 2 functional group in the contained ionizing radiation curable compounds of described coating fluid is that 50 quality % are above and below 95 quality %,
In described hard coat, containing median size is the particle more than 10nm and below 300nm,
The content of described particle in hard coat is more than 5 quality % and below 70 quality %.
2. hardcoat film for molding as claimed in claim 1, wherein, at least a kind of the contained ionizing radiation curing compound of described coating fluid for having amino ionizing radiation curing compound.
3. hardcoat film for molding as claimed in claim 1, wherein,
In described hard coat, contain ionizing radiation curing type silicone resin,
The content of described ionizing radiation curing type silicone resin in hard coat is more than 0.15 mass parts and below 15 mass parts with respect to described ionizing radiation curable compounds 100 mass parts.
4. a formed body, forms the hardcoat film for molding moulding described in any one in claim 1～3.
5. formed body as claimed in claim 4, wherein, the thickness of hard coat is more than 0.5 μ m and below 50 μ m.
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